Photographic developing compositions



United States Patent 3,265,502 PHDTOGRAPHIC DEVELOPING COMPOSITIONS Jozef Frans Willems, Wilrijk-Antwerp, and George Frans Van Veelen, Mortsel-Antwerp, Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel-Antwerp, Belgium, a company of Belgium No Drawing. Filed June 20, 1962, Ser. No. 203,750 Claims priority, application Belgium, June 21, 1961, 40,745, Patent 605,204 3 Claims. (Cl. 96---66) This invention relates to a process for the development of a latent image of exposed silver halide salts and to developing compositions used therein.

It is known that the developing activity of a developing solution containing a mixture of several developing substances, can be higher than the sum of the developing activities of the separate developing solutions of each of these developing substances used in the same concentration as in that mixture. This phenomenon is called the superadditive development.

Superadditive development is obtained with the combination of p-monomethylarninophenol hemisulphate and hydroquinone which has been described by G. Pizzighelli, Leitfaden der praktischen Photographic, Auflage 14 (Paul Hanneke), p. 177.

Further it is known from the British patent specification No. 542,502, that the mixture of hydroquinone and 1-phenyl-3-pyrazolidone has a still more intense developing action than the mixture of hydroquinone and pmonomethylaminophenol hemisulfate.

It is also known from the German patent specification No. 969,677 that dialkyl-p-phenylene diamine activates developers having a weak developing activity.

It is an object of this invention to provide a method for superadditive development by treating an exposed silver halide emulsion layer with a developing composition comprising hydroquinone and a p-phenylene diamine derivative as described hereinafter.

A further object of this invention is to provide developing compositions comprising hydroquinone and a p-phenylene diamine derivative as described hereinafter.

More particularly it is an object of this invention to provide developing baths containing a mixture of hydroquinone and a p-phenylene diamine derivative possessing super-additive developing properties, said pphenylene diamine derivative having a polarographic half-Wave potential which is at least 40 mv. more negative (according to the Europen Convention) than that of N,N-diethyl-p-phenylene diamine, and corresponding to a general formula selected from the group consisting of a, anon-Y 'wherein:

ice

group such as a hydroxyl group, but an integer of at least 3 and at most 8 when Y represents a sulfonic acid group wherein:

Each of R and R represents a member selected from the group consisting of an alkyl radical such as an ethyl radical and a substituted alkyl radical such as a hydroxyethyl radical, and

X represents an electro-negative group suchas an amino group, a monoalkylamino group, a dialkyl amino group, a sulfonamido group and an alkoxy group, and

( R5 I l N m-g-R...

wherein:

R represents a member selected from the group consisting of a hydrogen atom and an alkyl radical,

Each of R and R represents a member selected from the group consisting of a hydrogen atom and an alkyl radical,

m represents an integer from at least 2 and at most 3,

and

X represents a member selected from the group consisting of a hydrogen atom, an alkyl radical and anelectronegative group such as an amino group, a monoalkylamino group, a dialkyl amino group, a sulfonamido group and an alkoxy group.

These compounds can be added to the developing bath in the form of free bases as well as in the form of their salts.

The following are examples of these compounds.

(a) Compounds according to general Formula I:

(1) N,N,N,N' tetramethyl p phenylene diamine dihydrochloride (2) N,N,N',N'-tetraethyl-p-phenylene diamine dihydrochloride (3) N,N-diethyl-N,N-dimethyl-p-phenylene diamine dihydrochloride (4) N,N diethyl N Z-hydroxyethyl N ethyl pphenylene diamine disulfate (5) N,N diethyl N 4 sulfobutyl N ethyl pphenylene diamine (b) Compounds according to general Formula II:

(6) 4-diethylamino-2-amino-aniline sulfate (7) 4-diethylamino-2-methylamino-aniline sulfate (8) 4-diethylamino-2-methylsulfonamido-aniline (9) 4-diethylamino-2-ethoxyaniline hemisulfate (c) Compounds according to general Formula III:

(10) 6 amino 1 methyl 1,2,3,4 tetrahydroquinoline oxalate (11) 6 amino 1 (4 sulfoybutyl) 1,2,3,4 tetrahydroquinoline (12) 9-aminojulolidine sulfate.

Compound At pH 8 At pH 11 No. Amv. Amv

117 mv. 109 my.

'265 iil'v" 141 mv --79 my 40 mv -80 mv The preparations of many of these compounds are de scribed in J. Am. Chem. Soc. 73 (1951) pp. 31003125.

Compound is prepared by the alkylation of N,N,N'- triethyl-p-phenylene diamine =with butane sultone.

Compound 11 is prepared by the alkylation of tetrahydroquinoline with butane sultone followed by coupling with the diazonium salt of 2,4-dichloroaniline and reduction of the azo dyestufl.

Said compounds are weak developing agents if used in the absence of hydroquinone.

Besides derivatives of p-p-henylene diamine as described above and hydroquinone, a developing bath according to this invention may also contain ingredients such as buffer compositions which may comprise salts such as carbonates, borates, phosphates, bisulfites, metabisulfites, sulfites and acids such as boric acid and citric acid. The developing bath may further contain potassium bromide, water-softening agents such as polyphosphates or derivatives of ethylene diamine tetraacetic acid, antifogging agents and moistening agents, as well as other compounds known in the developing technique.

The pH of the baths can vary within wide limits, preferably between 8 and 11, so that a quick and hard development or a slow and soft development can be obtained at will.

The ratio of hydroquinone to a p-phenylene diamine derivative used in the present invention, can be chosen in such a way that the bath composition is suited for the development of all kinds of materials including materials having silver chloride emulsion layers of low sensitivity as well as materials having highly sensitive silver brornoiodide emulsion layers.

The ratio of hydroquinone to the p-phenylene diamine derivatives used in the present invention can vary Within lwide limits. The amounts are, however, generally chosen in such a way that the hydroquinone strongly outweighs the said p-phenylene diamine derivatives.

A strong superadditive effect is already obtained with a ratio of 50 mg. of a p-phenylene diamine derivative used in this invention to 5 g. of hydroquinone per litre. Larger amounts can also be used, although the superadditive effect which is obtained with concentrations of 1 to 2 g. of said p-phenylene diamine derivative and 5 to g. of hydroquinone per litre, is not much higher than With concentrations which are 10 times lower.

The developing solutions according to this invention, containing a combination of developing agents as described above, show with regard to the developing combination of hydroquinone and p-monomethylaminophenol hemisulfate the advantage that for a same developing activity a lower concentration of developing agents can be used. The developing agents used in the present invention show more particularly with regard to the developing combination of hydroquinone and l-phenyl-B-pyrazolidone the advantage of being stable to hydrolysis, even in strong alkaline medium.

The following examples illustrate the present invention.

Example I Strips of a photographic material comprising a lightsensitive silver bromoiodide emulsion layer, coated onto a cellulose triacetate support, are exposed through a grey filter with a light-quantity (E) which corresponds to the shoulder part of the density/log E curve.

Each of these exposed strips are developed at 20 C. in separate developing baths. One of them is developed in a bath A containing as developing agent only hydroquinone and having the following composition:

G. Boric acid 5 Borax 10 Sodium hexamet-aphosph-ate 1 Sodium sulfite 20 Hydroquino-ne 4.4

Water up to 1000 cm.

The other strips are respectively developed in baths, having the same composition as bath A but containing moreover an equivalent amount of a developing agent as listed in Table 1 given hereinafter. The densities are determined respectively after a developing time of 1, 3, 5

and 10 min.

TABLE 1 Density (D) Developing time 1 min. 3 min. 5 min. 10 min.

Bath A 0. 04 0. 04 0. O4 0. 04 Bath A+50 mg. of 1-phenyl-3- pyrazolidone 0.07 0.92 1. 93 Bath A+81 mg. of N,N-diethylp-phenylene diamine sulfate. 0. 05 0. 42 1. 10 1. 55 Bath A+ mg. of triethyLpphenylenediamine dihydrochloride 0. 25 1. 30 Bath A+ mg. of compound 2 0. 60 1. 50 Bath A+133 mg. of compound 4... 0.30 1. 17 Bath A+102 mg. of compound 5. 0. 10 1. 10

Example 2 Strips of a photographic material comprising a lightsensitive silver bromoiodide emulsion layer, coated on a cellulose triacetate support, are exposed through a grey filter with a light-quantity ('E) which corresponds to the shoulder part of the density/ log E curve.

One of these film strips is developed in a bath B having the following composition:

Sodium carbonate 20 Sodium hexametaphosphate 1 Sodium sulfite 20 Potassium bromide 0.5 Hydroquinone 4.4

Water up to 1000 cm.

The other strips are respectively developed in baths having the same composition as bath B but moreover containing an equivalent amount of a developing agent as listed in Table 2 given hereinafter.

In order to show the superadditive character of the development with the combinations of hydroquinone and the p-phenylene diamine derivatives used in this invention, film strips, which are exposed in the same way as the above film strips, are developed in the same baths containing, however, no hydroquinone. A bath having the same composition as bath B but containing no hydro quinone is called bath C. The results of these developing tests are given in Table 3. All these developments take place at 20 C. The densities are determined respectively after a developing time of 30, 60, 90 and 120 sec.

TABLE 2 Density (D) Developing time 30 sec. 60 sec. 90 sec. 120 sec.

Bath B 0. 04 0. 04 0. 0. 18 Bath B 50 mg. of l-phenyl-S- pyraz'olidonc 0. 24 1.75 Bath B 81 mg. of diethylphenylenediaminesulfate 0.04 0. 05 0. 14 0. 32 Bath B 80 mg. of tricthyl-pphenylenediamine dihydrochloride 0. 11 0. 60 1. 3O 2. 10 Bath B 90 mg. of compound 2... 0. 22 0.80 1. 80 2. 50 Bath B 133 mg. of compound 4... 0.23 0. 86 2.00 Bath B 102 mg. of compound 5.. 0.13 0. 20 0. 40 1 Bath B 85 mg. of compound 6.-- 0. 53 1.80 Bath B 95 mg. of compound 7... 1. 00 2.00 Bath B 84 mg. of compound 9... 0.09 0. 27 0.80 1. 40 Bath B 70 mg. of compound 10.. 0.10 0. 40 1. 10 1.75

TABLE 3 Density (D) Developing time 30 sec. 60 sec. 90 see. I 120 sec Bath 0 0. 04 0. 04 0. 04 0. 04 Bath 0 50 mg. 1-phenyl-3- pyrazohdone 0. 04 0.05 O. 10 0. 13 Bath 0 81 mg. diethyl-p-phenylcne diamine sulfate 0. 04 0.06 0.08 0. 10 Bath 0 80 mg. triethyl-p phenylene 'diamine dihydro chloride 0. 04 0.10 0. 12 O. 15 Bath 0 90 mg of compound 2..-. 0. O4 0. 04 0.06 0.06 Bath 0 133 mg. of compound 4.. 0. 04 0. 04 O. 06 0. 10 Bath 0 102 mg. of compound 5.. 0. 04 0.04 0. 06 0.10 Bath 0 85 mg. of compound 6.-. 0.06 0.12 0. 16 0.20 Bath C 95 mg. of compound 7... 0.06 0. 12 0.16 0.20 Bath 0 84 mg .of compound 9... 0. 04 0.07 0. 11 0. 14 Bath 0 70 mg. of compound 10.. 0. 04 0.07 0.11 0.14

Example 3 Boric acid 5 Borax 10 Sodium hexametaphosphate 1 Sodium sulfite 20 Potassium bromide 0.5 Hydroquinone 4.4

Water up to 1000 cm.

The other strips are respectively developed in developing baths having the same composition as bath D, but containing moreover an equivalent amount of a developing agent as listed in Table 4 given hereinafter.

The densities are respectively determined after 1, 3 and 5 min.

TABLE 4 Density (D) Developing time 1 min. 3 min. 5 min.

Bath D 0. 04 0. 04 0. 04 Bath D+85 mg. of compound 6... 0.20 0.67 1.00 Bath D+95 mg. of compound 7... 0. 21 0. 52 0.78 Bath D+70 mg. of compound 9 0. 04 0. 27 0. 68

In order to show the superadditive character of the development with the combinations of hydroquinone and the p-phenylene diamine derivatives used in this invention, film strips, which are exposed in the same way as the above film strips, are developed in the same baths containing, however, no hydroquione. A bath having 5 the same composition as bath D but containing no hydroquinone is called bath E. The results of these developing tests are given in Table 5. All developing tests were carried out at 20 C. and the densities determined after 1, 3 and 5 min.

What is claimed is:

1. Photographic developing solution comprising hydroquinone and a derivative of p-phenylene diamine having a pol-arographic half-wave potentialwhich is at least 40 mv. more negative than that of N,N-diethyl-p-phenylene diamine and corresponding to a general formula selected from the group consisting of:

I a (C 2)n' wherein:

each of R R and R represents a lower alkyl radical, Y represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, and a sulfonic acid group and salts thereof, n represents an integer of at least 2 and at most 8 when Y represents a hydrogen atom or a hydroxyl group; and an integer of at least 3 and at most 8 when Y represents a sulfonic acid group,

(II) R1 R2 l lHz wherein: each of R and R represents a member selected from the group consisting of an alkyl radical a lower and a hydroxy-substituted lower alkyl radical, and X represents an electro-negative group selected from the group consisting of an amino group, a monoalkylamino group, a dialkylamino group, a sulfonamido group and an alkoxy group;

n) R5\ f 6 R7)m NHz 7 wherein:

R is a lower alkyl radical,

R and R each represent a member selected from the group consisting of a hydrogen atom and a lower alkyl radical,

m represents an integer of at least 2 and at most 3, and

X represents a member selected firom the group consisting of a hydrogen atom, a lower alkyl radical, an amino group, a monoalkylamino group, a dialkyl amino group, a sulfonam-ide group and an alkoxy (IV H3 H;

H2O N (13H; HZC 1 CH2 wherein:

X represents a member selected from the group consisting of a hydrogen atom, a lower alkyl radical, an amino group, a sulfonamido group and an alkoxy p;

(V.) and the salts thereof.

2. Photographic developing solution containing per liter from 5 g. to g. of hydroquinone and from 50 mg. to 2 g. of a p-phenylene diamine derivative having a polarographic half-wave potential which is at least 40 mv. more negative than that of N,N-diethyl-p-phenylene diamine and corresponding to a general formula selected from the group consisting of:

I a (O 2)nY wherein:

each of R R and R represents a lower alkyl radical,

Y represents a member selected from the group consisting of a hydrogen atom a hydroxyl group, and a sulfonic acid group and salts thereof,

n represents an integer of at least 2 and at most 8 when Y represents a hydrogen atom or a hydroxyl group; and an integer of at least 3 and at most 8 when Y represents a sulfonic acid group;

wherein:

each of R and R represents a member selected from the group consisting of a lower alkyl radical and a hydroxy substituted lower alkyl radical, and

X represents an electro-negative group selected from the group consisting of an amino group, a monoalkylamino group, a dialkylamino group, a sulfonamido group and an alkoxy group;

(III) I r Rs- (Rab-Rfl m X N H2 wherein:

m represents an integer of at least 2 and at most 3, and X represents a member selected from the group consisting of a hydrogen atom, a lower alkyl radical, an amino group, a monalkylamino group, a dialkyl amino group, a sulfonamide group and an alkoxy group; and

(IV) H2 H2 H N (IJHZ H20 I OH:

wherein:

each of R R and R represents a lower alkyl radical,

Y represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group and a sulfonic acid group in free acid and salt form,

n represents an integer of at least 2 and at most 8 when Y represents a hydrogen atom or a hydroxyl group, but an integer of at least 3 and at most 8 when Y represents a sulfonic acid group;

NH; wherein:

each of R and R represents a member selected from the group consisting of a lower alkyl radical and .a hydroxy-substituted lower alkyl radical, and X represents an electro-negative group selected from the group consisting of an amino group, a monoalkylamino group, a dialkylamino group, a sulfonwherein:

amido group and X represents a member selected from the group conan alkoxy group; sisting of a hydrogen atom, a lower alkyl radical, an amino group, a sulfonamido group and an alkoxy (III) 1 5 group; RFN (V.) and the salts thereof.

References Cited by the Examiner X UNITED STATES PATENTS 1 2,848,326 8/1958 Whitrnore 96-29 wherein: FOREIGN PATENTS m represents an integer of at least 2 and at most 3, 969 677 7/1958 Germany and X represents a member selected from the group con- OTHER REFERENCES slsting of a hydrogen atom 9 alkyl radlc'fll an Axford: Journal Photographic Science, vol. 7, pp. 120-5 .arnlno group, a monoalkylamlno group, a dialkyl (1959) amino group" a Sulfonamide group and an alkoxy Jaenicke et al.: Z. Elektrocheim vol. 63 pp. 722-36 group; and (1959). g 5, James: PSA Journal, vol. 19B, pages 156-60 1953 Levenson: Photographic Journal, vol. 92B, pp. 109-10 (1952). (LE: Ulrich et al.: Photographic Science and Engineering, vol. 4, pages 2258 (1960).

NORMAN G. TORCHIN, Primary Examiner.

H2 J. T. BROWN, Assistant Examiner. 

1. PHOTOGRAPHIC DEVELOPING SOLUTION COMPRISING HYDROQUINONE AND A DERIVATIVE OF P-PHENYLENE DIAMINE HAVING A POLAROGRAPHIC HALF-WAVE POTENTIAL WHICH IS AT LEAST 40 MV. MORE NEGATIVE THAN THAT OF N,N-DIETHYL-P-PHENYLENE DIAMINE AND CORRESPONDING TO A GENERAL FORMULA SELECTED FROM THE GROUP CONSISTING OF: 